Five 8,11-substituted pentacyclo[5.4.0.02,6.03,10.05,9]undecanes

Abstract

1) 11 -Bromo-11 -nitropentacyclo-[5.4.0.02'6.03' t °.05'9]undecane-8-one, Ci iHloBrNO3, Mr= 284-11, monoclinic, P2~/n, a = 11.155 (3), b = 8.180(2), c=12.387(3) A, /3 =113.54 (2) ° , V= 1036.2 (5) ,~3, Z = 4, Dx = 1.82 Mg m -3, A(Cu Kce) =1.54184~, tx=5-39mm-I, F(000)=568, T= 295 K, R = 0.038 for 1384 unique observed reflections.(2) 8,11-Dibromo-8,11-dinitropentacyclo[5.4.0.0x6.03"l°.05"9]undecane, CiiHioBr2N204, Mr = 394.03, monoclinic, P21, a= 6.788 (2), b= 13.696 (4), c= 6.931 (2) A, /3 = 107.19 (2) °, V= 615-5 (3) A 3, Z = 2, Dx = 2-13 Mg m -3, A(Cu K~e) = 1.54184 A, /1, = 8.58 mm-~, F(000) = 384, T= 295 K, R = 0.041 for 1003 unique observed reflections.(3) 8,11-Dichloro-8,11 -dinitropentacyclo[5.4.0.02"6.03"l°.05"9]undecane, CliHioC12N204, Mr = 305-11, monoclinic, P21, a = 6.773 (3), b= 13.579 (7), c=6.834(4)~, /~=107.24(4) °, V = 600.3 (6) A 3, Z = 2, Dx = 1.69 Mg m-3, a(Mo Ka) = 0-71073 A, /z =0.55mm-~, F(000) = 312, T= 295 K, R = 0.039 for 969 unique observed reflections. (4) 8,11 -Dinitropentacyclo[5.4.0.02'6.03"l 0.05"9]undecane, CIIHI2N204, Mr=236-22, monoclinic, P21/c, a = 8.530 (1), b = 9.909 (1), c = 12-277 (1) A, /3=96.52(2) ° , V =1031.0(2) A 3, Z =4, Ox= 1.52 Mg m -3, A(Cu Ka) = 1.54184 ~, # = 0-95 mm-l, F(000) = 496, T = 295 K, R = 0.048 for 1363 unique observed reflections. (5) 8,8,11,11-26 3 10 59

3,5-Bis(2-hydroxyethyl)-4-oxahexacyclo[5.4.1.02,6.03,10.05,9.08,11]dodecane

“…1), the shortening or elongation of specific C-C bonds, as reported previously for related compounds, is also observed. The C9-C10 bond is long with a value of 1.568 (2) Å , which is shorter than values reported for cage compounds in which atoms C8 and C11 are not linked by the oxo bridge; for example, values of 1.579 (4), 1.600 (7) and 1.585 (4) Å have been reported (Flippen-Anderson et al, 1991). The C2-C6 and C1-C7 bonds, which form part of the cyclobutyl group, are also long, with values of 1.567 (2) and 1.553 (2) Å , respectively.…”

“…The molecular geometries of PCU cage derivatives have been reported in a number of studies, and are of interest because certain bonds tend to be longer or shorter than the value of 1.54 Å expected for a C-C single bond (see, for example, Flippen-Anderson et al, 1991;Linden et al, 2005). In particular, the C9-C10 bond has been found to be abnormally long, whereas the bonds connecting atoms C8 and C11 to the cage, as well as the bonds involving atom C4, are often shorter than normal.…”

8,11-Dihydroxypentacycloundecane-8,11-lactam

“…1). A number of publications have focused on the molecular geometries of PCU cage derivatives (Flippen-Anderson et al, 1991;Linden et al, 2005;Kruger et al, 2005), and it has been reported that these compounds exhibit C-C bond lengths deviating from the normal value of 1.54 Å .…”

Crystal structures of 3,6-diallyltetracyclo[6.3.0.04,11.05,9]undeca-2,7-dione and 1,7-diallylpentacyclo[5.4.0.02,6. 03,10.05,9]undecane-8,11-dione: allylated caged compounds

“…The C-C strained bond angles in (1) vary from 95.31 (10) to 125.21 (14) , deviating from the ideal tetrahedral angle of 109.5 . Previous studies showed that PCUD caged compounds normally display C-C bond lengths which deviate from expected value of 1.54 Å (Bott et al, 1998;Flippen-Anderson et al, 1991;Linden et al, 2005;Kruger et al, 2005). The structure of (1) also exhibits unusual Csp 3 -Csp 3 single-bond lengths ranging from 1.5092 (19) Å to 1.5935 (19) Å .…”